Conversion of olefins using complexes of fe,ru,os,rh or ir with organoaluminums

ABSTRACT

A process for the conversion of olefinic hydrocarbons according to the olefin reaction (e.g., the olefin disproportionation reaction) by contacting the olefinic hydrocarbon with a catalyst comprising a compound of ruthenium, iron, osmium, rhodium, cobalt or iridium complexed with a selected complexing agent (e.g., triphenylphosphine) and combined with an organoaluminum compound (e.g., methylaluminum sesquihalide). A process of preparing rhodium and iridium NO-containing complexes is described. Metal complexes which contain both NO and NO2 complexing agents are also described.

United States Patent- [191 Hughes et a1.

]March 20, 1973 [s41 CONVERSION OF OLEFINS USING COMPLEXES OF Fe, Ru, Os, Rh OR Ir WITH ORGANOALUMINUMS 7s 1 Inventors: William B. Hughes; Ernest A.

Zuech, both of Bartlesville, Okla.

[73]. Assignee: Phillips Petroleium Company, Bartlesville, Okla.

22 Filed: Sept. 17', 1970 21 Appl. No.2 73,232

Related U.S. Application Data [60] Division of Ser. No, 810,021, March'24, 1969, Pat. No. 3,558,517, which is a continuation-in-part of Ser.

No. 717,025, March 28, 1968, abandoned, which is a continuation-in-part of Ser. No. --696,109, Jan. 8,

1968, abandoned, which is a continuation-impart of I 1 Ser. No. 635,688, May 3, 1967, abandoned.

[52] U.S. Cl ..260/683 D, 260/94.9 13, 260/666 A, 260/677 R, 260/680 R, 260/683.15 D,

1]. Int. CL; .l ..C07c 3/62 8] Field of Search ..260/666 A, 6 77, 680, 683 D, 260/94.9 B, 683.2, 651, 658, 683.15 D

I 1 References Cited UNITED STATES PATENTS 3,390,201 6/1968 Drew ..260/683.15 3,482,001 12/1969 Eberhardt 260/683 15 3,376,706 4/1968 Wilke 260/683 15 3,450,732 6/1969 Wi1ke et a1. ..252/431 3,457,319 7/1969 Olechowski et a1. ..260/677 3,409,681 11/1968 Kroll ..260/683.2

Primary Examiner-Delbert El Gantz Assistant Examiner-C. E. Spresser Attorney-Young and Quigg 57 ABSTRACT A process for the conversion of olefinic hydrocarbons according to the olefin reaction (e.g., the olefin dis-' 20 Claims, No Drawings CONVERSION OF OLEFINS'USING (ItQlt/llPlLEXES F Fe, Ru, Os, Rh OR Ir WITH ORGANOALUMINUMS- This application is a division of copending application Ser.- No. 810,021, filed Mar. 24, 1969, now U.S. Letters Pat. No. 3,558,517 issued Jan. 26, 1971, which is a continuation-in-part of application Ser. No. 717,025, filed Mar. 28, 1968, now abandoned, which is a continuation-in-part of application Ser. No. 696,109, filed Jan. 8, 1968, now abandoned, and which is a continuation-in-part of application Ser. No. 635,688, filed May 3, 1967, now abandoned.

This invention relates to the conversion of olefin hydrocarbons and to a catalyst system for such conversion. In one aspect this invention relates to the olefin reaction. In another aspect it relates to the conversion of olefins to other olefins having different molecular weights. In still another aspect it relates to a-novel, homogeneous, multi-component complex catalyst. In still a further aspect it relates to a new method of preparing complex compounds of transition metals. In still a further aspect it relates to new complex compounds of transition metals.

The term olefin reaction, as used herein, is defined as a process for the catalytic conversion in the presence of a catalyst of a feed comprising one or more ethylenically unsaturated compounds to produce a resulting product which contains at least ten per cent by weight of product compounds, which product compounds can be visualized as resulting from at least one primary reaction, as defined. below, or the combination of at least one primary reaction and at least one unsaturated bond isomerization reaction, and wherein the sum of the compounds contained in said resulting product consisting of hydrogen, saturated hydrocarbons, and compounds which can be visualized as formed by skeletal isomerization but which cannot be visualized as formed by one or more of the above-noted reactions, comprises less than per cent by weight of the total of said resulting product. Feed components and unsaturated bond isomers thereof are not included in the resulting product for the purpose of determining the above-noted percentages.

In the olefin reaction, as defined above, the primary reaction is a reaction which can be visualized as comprising the breaking of two existing unsaturated bonds between first and second carbon atoms and between third and fourth carbons atoms, respectively, and the formation of two new unsaturated bonds. Said first and second carbon atoms and said third and fourth carbon atoms'can be in the same or different molecules.

The olefin reaction according to this invention is illustrated by the following reactions:

l. The disproportionation of an acyclic monoor polyene having at least three carbon atoms into other acyclic monoor polyenes of both higher and lower number of carbon atoms; for example, the disproportionation of propylene yields ethylene and butenes; the disproportionation of 1,5-hexadiene yields ethylene and 1,5,9-decatriene;

2. The conversion of an acyclic monoor polyene having three or more carbon atoms and a different acyclic monoor polyene having three or more carbon atoms to produce different acyclic olefins; for example, the conversion of propylene and isobutylene yields ethylene and isopentene;

3. The conversion of ethylene and an internal acyclic monoor polyene having four or more carbon atoms to produce other olefins having a lower number of carbon atoms than that of the acyclic monoor polyene; for example, the conversion of ethylene and 4-methylpentene-2 yields 3-methyl-butene-1 and propylene;

' 4. The conversion of ethylene or acyclic monoor polyene having three or more carbon atoms and a cyclic monoor cyclic'polyene to produce an acyclic polyene having a higher number of carbon atoms than that of any of the starting materials; for example, the conversion of cyclooctene and Z-pentene yields 2,10-

tridecadiene; the conversion of 1,5-cyclooctadiene and ethylene yields 1,5 ,9-decatriene;

5. The conversion of one or more cyclic monoor cyclic polyenes to produce a cyclic polyene having a higher number of carbon atoms than any of the starting materials; for example, the conversion of cyclopentene yields l,6-cyclodecadiene and continued reaction can give higher molecular weight materials;

6. The conversion of an acyclic polyene having at least seven carbon atoms and having at least five carbon atoms between any two double bonds to produce acyclic and cyclic mono and polyenes having a lower number of carbon atoms than that of the feed; for example, the conversion of 1,7-octadiene yields cyclohexene and ethylene; or

7. The conversion of one or more acyclic polyenes having at least three carbon atoms between any two double bonds to produce acyclic and cyclic monoand polyenes generally having both a higher and lower number of carbon atoms than that of the feed material; for example, the conversion of 1,4-pentadiene yields 1,4-cyclohex'adiene and ethylene.

New catalytic processes have been discovered in recent years for the conversion of olefins to other olefinic products including products of both higher and lower molecular weight whereby olefins of relatively low value are converted into olefins of higher value. Such conversions have heretofore been carried out using heterogeneous catalysts comprising compounds such as compounds of molybdenum or tungsten and generally associated with materials such as alumina or silica. It has now been found that these olefin conversions can be carried out in a substantially homogeneous stage using, as catalyst, selected coordination comdiscovered new rhodium or iridium complexes which in combination with the catalytic adjuvant materials provide a catalyst which is capable of producing olefin products of increased value.

Further in accordance with the invention, we have discovered an improved method for the preparation of certain rhodium and iridium complexes which, when combined with suitable catalytic adjuvants, form a catalyst capable of providing olefin products of increased value.

It is an object of this invention to provide a method and a homogeneous catalyst for the conversion of olefin hydrocarbons. It is also an object of this invention to provide a homogeneous catalyst comprising a coordination complex of ruthenium, iron, osmium, cobalt, rhodium or iridium together with an aluminumcontaining adjuvant for the conversion of olefin hydrocarbons.

It is a further object of the invention to provide an improved method of preparing coordination complexes of rhodium and iridium. Still another object of the invention is to provide new complexes of rhodium and iridium which, together with an aluminum-containing adjuvant, are capable of converting olefin hydrocarbons.

A further object is to provide a homogeneous catalyst for the olefin reaction. Still another object is to provide a method for converting olefins to other olefins of higher and lower number of carbon atoms utilizing a homogeneous catalyst. The provision of a homogeneous catalyst for converting olefins to other olefins of higher and lower number of carbon atoms is yet another object of the invention. Other aspects, objects and advantages of the invention will be apparent to one skilled in the art upon study of the disclosure, including the detailed description of the invention.

According to the process of this invention, cyclic and acyclicolefins, preferably non-tertiary olefins, and mixtures of these, including mixtures with ethylene, are converted into other olefins with a catalyst system which forms by the admixture, under catalyst forming conditions, of components comprising a. a complex which forms, under complexforming conditions, of a compound of a metal of the iron or cobalt subgroups of Group VIII with at least on ligandforming material; and

b. an aluminum-containing catalytic adjuvant under conditions of time, temperature, and pressure suitable to form products different from the feed olefin.

The ligand-forming material of the metal complex of the (a) component is represented by the formula: NO; NOX; R R Q- QR R NR NR CO; compounds containing the radical (CHR C W Gl-Tf-f; unsubstituted or R -substituted pyridines; unsubstituted or R -substituted 2,2-bipyridines; unsub-.

stituted or R-substituted cyclopentadienyl radical-containing compounds;

, R-S-R, R-(CN),,, RflCOO-h, radical-containing compounds; l,5-cyclooctadiene; dicyclopentadiene; or norbornadiene, wherein X is halogen, R is an aromatic or saturated aliphatic hydrocarbon radical, including alkoxy and halo-substituted radicals, having up to 20 carbon atoms, R is hydrogen or R, R is a divalent R radical, R is a divalent saturated or ethylenically unsaturated aliphatic hydrocarbon radical having four to carbon atoms, R is hydrogen or a methyl radical; R is an aromatic, saturated or ethylenically unsaturated aliphatic radical having up to 30 carbon atoms, Q is phosphorus, arsenic or antimony, and y is an integer from 1 to 2.

The catalyst system of the invention can further be illustrated by the following formulas, i.e., the catalyst system consists of a. a metal complex represented by the formula:

wherein M is a metal of the iron or cobalt subgroups of Group Vlll, namely iron, ruthenium, osmium, cobalt, rhodium, and iridium; each 2 is halogen or CN, SCN, OCN, SnCl or an organic .acid radical having up to about 30 carbon atoms; each (Y) is NO or a (CHR dicyclopentadiene, or norbornadiene; a is 0-6, b is 1-2,

y is l-2, but when y is 2, R of the R (CN),, and R-*(GOO) is a divalent radical and as otherwise defined; 0 is l-3, d is 0-6, x is a number which is indicative of the polymeric state of the complex, and wherein the number of (L), (Y), and Z groups present in the complex is not greater than the number required for the metal to achieve the closed shell electronic configuration of the next higher atomic number inert gas; when M is Ru or Os, b is 2-2; when M is Fe, (Y) is NO and b is 2; R is an aromatic or saturated aliphatic hydrocarbon radical, including alkoxy and halo-substituted radicals, having up to 20 carbon atoms; R is hydrogen or R; R is a divalent R radical; R is a divalent saturated or ethylenically unsaturated aliphatic hydrocarbon radical having from four to 10 carbon atoms; R is hydrogen or a methyl radical; R is an aromatic, saturated aliphatic, or ethylenically unsaturated aliphatic radical having up to 30 carbon atoms; and Q is phosphorus, arsenic or antimony; with b. an aluminum-containing catalytic selected from 2. a mixture of compounds of( l adjuvant 3. a mixture of one or more R AlX, or AlX compounds with one or more compounds having the I formula R,, M'X or 4. an AlX compound wherein each Ris an aromatic or saturated aliphatic hydrocarbon radical having up to 20 carbon atoms including alkoxy and halo derivatives thereof, preferably an alkyl radical having up to l0 carbon atoms; each R is hydrogen or R; each X is a halogen; each M is a metal of Group lA, A, B, or MIA; 2 is 1, 2 or 3,fis 0,1 or 2, the sum ofeandfbeing 3;gis l, 2 or 3, h is 0,1 or 2, the sum ofg and It being equal to the valence of M; when the adjuvant is (l) and acyclic olefins are converted, f is preferably 1 or 2.

Further according to the invention, nitro-nitrosyl complexes of rhodium or iridium of the type (R Q) M (NO)(NO )X are provided wherein Q is phosphorus or arsenic, M is rhodium or iridium, and R and X are as described previously. These novel nitronitrosyl complexes may be used as the (a) component of the catalyst system of the invention.

Still another feature of the present invention is an improved method of preparing complex compounds of the type (R Q) M (NO)X, a) by reacting compounds of the type M X with NO followed by reaction of this reactionproduct with compounds of the type R Q or b) by reacting compounds of the type (R Q);,M X with NOX compounds wherein M R, Q, and X are as defined earlier.

The elements referred to herein are in accordance with the Periodic Table of Elements appearing in Handbook of Chemistry and Physics, Chemical Rubber Co., 45th Edition (1964).

Some specific examples of R,AlX, and Alx compounds are: methylaluminum sesquichloride, methylaluminum dichloride, dimethylaluminum fluoride, ethylaluminum. dichloride, aluminum trichloride, ethylaluminum sesquichloride, diethylaluminum chloride, di(3-ethoxypropyl)aluminum bromide, aluminum tribromide, di(methoxymethyl)aluminum bromide, di-(2-ethylhexyl)aluminum bromide,

phenylaluminum dichloride, benzylaluminum diiodide,.

di(4,4,4-trifluorobutyl)aluminum chloride, dieicosylaluminum bromide, and the like, and mixtures thereof.

Some specific examples of the R,,MX,, compounds are: phenyllithium, t-butylpotassium, methylsodium benzylrubidium, lithium hydride, anthrylce's ium, lithium aluminum hydride, diethylberyllium, lithium borohydride, methylcadmium chloride, diethylzinc,

dicyclohexylmercury, triethylalum'inum, methylgallium dibromide, triethylindium, di( l2-chlorododecyl)aluminum chloride, n-butyl-boron difluoride, hexylzinc iodide, triisopropylthallium, dimethylcalcium, dimethylstrontium, diethylbarium, and the like, and mixtures thereof.

The preferred (b) components of the catalyst system are'adjuvants selected from (l) or (2).

The Group Vlll metal complex (a) components of the catalyst systemcan be formed by the admixture,

under complex forming conditions of a compound of a suitable metal found in the iron or cobalt subgroups of .Group VIII such as a halide, carbonyl, carbonyl halide, or salt of an inorganic or organic acid, preferably a halide, with one or more complexing agents represented by NO, NOX, (CHR =CR CH2) radical-contain- R -NR CO, unsubstituted or R -substituted pyridines, unsubstituted or R -substituted 2,2- bipyridines, unsubstituted or R-substituted cyclopentadienyl radical-containing compounds,

.R-S-R, .R (CN)," R (COO-- radical-containing compounds, 1,5-cyclooctadiene, dicyclopentadiene, or norbornadiene, wherein X is a halogen and R, R, R R, R, R", b, y and Q are as previously defined, and

wherein at least one of NO, NOX or (CHR*-=CR CH-2+ radical-containing compounds are in the admixture when cobalt, rhodium, or iridium compounds are used, and wherein atleast one of NO or NOX are in the admixture when iron compounds are used.

Frequently preferred metal complex (a) cornponents are those which contain halogen atoms. Consequently, it is frequently desirable to use nitrosyl halides in methyldicyclohexylstibine;

preference to NO when forming the metal complex as shown above. Nitrosyl halides, however, can be used if desired, even though the Group VIII starting compound is a halide.

Some examples of suitable Group VIII starting compounds are pecla, FC(CO)5, Fe(CO)5Cl2, Fe(CO)2Ig, Fe (CO) FeB 'a, F FQ, Fe (oxalate) Fe(CNS) [lr(CO) lr(CO) Br, lr(CO) Cl,, and the like, and mixtures thereof.

Some examples of suitable complexing agents are: tri-n-butylphosphine; tri-n-decylphosphine; tri-neicosylphosphine; methyl-di-n-octylph osphine;' tricyclohexylphosphine; triphenylphosphine; tribenzylphosphine; triethylarsine; triisopropylarsine; tri-n-pentadecylarsine; diethyl-n-tridecylarsine; tricyclopentylarsine; diethylphenylarsine; tri(3,6-diphenyloctyl)arsine; tri-tbutylstibine; tri-n-nonylstibine; tri(6,8-di-n-butyldecyl)stibine; tri(3,S-dimethylcyclohexyl)stibine;

tri(2,4,6-triethylphenyl)stibine; methyldi(4-dodecylphenyl)stibine; nitrosyl chloride; nitrosyl bromide, nitric oxide, tetramethyldiphosphine, tetrabutyldiarsine, tetradecylidiphosphine, tetraphenyldistibine, tetrabenzyldiphosphine, tetracyclopentyldiphosphine, tetraethyldiarsine, acetic acid, propionic acid, butanoic acid, Z-methylpropionic acid, pentanoic acid, octanoic acid, oxalic acid, benzoic acid, phenylacetic acid, malonic acid, acetonitrile, ethylenedinitrile, butyronitrile, 1,2-cyclohexylenedinitrile, sodium cyclopentadienylide, potassiummethylcyclopentadienylide, allyl bromide, methallyl chloride, crotyl bromide, tetrallyltin, tetramethallyltin,

ethylamine, .trimethylamine, triphenylamine, dibutylamine, N ,N,N ,N -tetramethylethylenediam ine N,N -dibenzylethylenediamine, l ,5-cyclooctadiene, dicyclopentadiene, norbornadiene, and the like, and mixtures thereof.

Some examples of suitable Group Vlll metal complex (a) components are:

tri(4-cyclohexylbutyl)arsine;

methallyl RhCl,

'ryidine)RhCl (1r -crotyl) (cyclopentadienyl)RhCl,

('zr-methallyl) (pyridine) RhCl (rr-allyl) (1,5- COD)Rh, NOCl-treated (triphenylphosphine) RhCl, NO-treated (triphenylphosphine) RhCl, NO-treated triphenylposphine-treated RhCl (tripehylphosphine) CoCl (4-vinylpyridine),CoCl NO-treated CO-treated RuCl CO-treated triphenylphosphinetreated RuCl ('rr-allyl) (cyclopentadienyl)lrBr, and the like, and mixtures thereof.

The formula [(L) (Y) M Z is used herein to identify the product obtained by the admixture, under catalyst forming conditions, of the metal compound with one or more ligand-forming materials whether or not the components are present in the complex as indicated in the formula.

When the (a) component of the catalyst system is the product obtained by combining a suitable Group VIII metal compound with one or more suitable ligandforming materials, these materials are simply combined under conditions of time and temperature which permit the complex'to be formed. In general, excessively high temperatures at which the reagents tend to decompose,

or excessively low temperatures, at which the reagents tend to crystallize or otherwise tend to become unreactive, should be avoided. The molar proportion of transition metal salt to the. selected ligand-former can be in the range of from about 0.1:] to about 10:1, preferably from about 0.521 to about 2:1. The products are obtained by combining these ingredients at a temperature preferably in the range of from about to about 130 C., more preferably 20 to about 60 C., for a time in the range of from a few seconds up to about 24 hours, preferably in the presence of a diluent in which the components of the admixture are atleast partially soluble. Any convenient diluent such as carbon tetrachloride, methylene chloride, xylene, cyclohexane, isooctane, benzene, chlorobenzene, and the like, can be used for this purpose. Any order of addition can be used. Such product need not be isolated but the mixture can be used directly in the formation of the catalyst system. In general, the (a) component of the catalyst system if fully prepared before contact is made with the (1)) component of adjuvant.

When the (a) component of the catalyst system is a rhodium or iridium complex of the type (R Q) M NO)(NO )X, starting compounds of the type (R3Q)aM X in a diluent such as that described above are treated with NO under conditions of time and temperature suitable for the formation of the desired nitronitrosyl complex. Preferably, an amount of NO is used which is somewhat is excess of the stoichiometric amount in order to increase the rate of formation of the new complex compound. In a similar manner, compounds of the type (R Q) M (CO)X can be reacted with NO to produce the nitro-nitrosyl complexes.

Still another method for obtaining these rhodium or iridium nitro-nitrosyl complexes is by reacting compounds of the type (R Q) M (CO)(NO,) with NOX compounds under conditions of time, temperature, and diluent as described above, except that in this reaction approximately stoichiometric amounts of NOX are preferred. Up to about a percent excess of the stoichiometric amounts of NOX can be tolerated. Thus, approximately one mole of NOX compound is used to react with each mole of (R Q),M (CO)(NO,) compound.

Suitable rhodium or iridium compounds which can be reacted with the NO or NOX compounds as shown above are commercially available or are conventionally prepared. For example, the (R Q) M X compounds can be suitably prepared by reacting wx, compounds with R 0 compounds at an elevated temperature in a suitable diluent such as ethanol. Compounds of the type (R -,Q M(CO)X can be prepared by reacting CO with compounds of the type (R Q) M X. Similarly, compounds of the type (R Q) M (CO)(NO can be conveniently prepared by reacting compounds of the type (R Q) M (CO)X with NaNO A new method of preparing compounds of the type (R Q' 2M (NO)X is to react compounds of the type M X}, including h arstes'fierar;tumor;a. solvent in which the M x, compound is at least partially soluble. Preferably, the solvent is an alcoholic solvent, such as ethanol. As with the complexes above, an excess of NO is frequently beneficial to increase the rate of the reaction. After the NO ceases to be absorbed by the metal salt, compounds of the type R 0 are simply added to the reaction mixture and allowed to react with the intermediate product previously formed.

Another convenient method of preparation of (B Q ')2M (N( ))X2 compounds is by reacting (R Q M compounds with NOX compounds in a MEET; inert diluent under conditions of time and temperature, generally described in paragraphs above, suitable for the preparation of the desired complex compound. Again, approximately stoichiometric amounts of NOX compounds are used, that is, about a 1:1 mole ratio with the metal compound, and preferably no more than about a 10 percent excess of the stoichiometric quantity.

When the formation of the (a) components of the catalyst system involves the use of alcohols or other solvents which might be reactive with the organoaluminum (b) components of the catalyst system, such solvents should be removed by evaporation and replaced by other inert solvents, for example halogenated hydrocarbons.

The molar proportion of the (b) component to the (a) component, to form the catalyst system of the present invention, will generally be in the range of from about 0. l :1 to 20:1, preferably from about 4:1 to about 10:1.

The catalyst is prepared simply by combining the (a) component and the (b) component under conditions of time and temperature which permit the catalytically active mixture to be formed, avoiding excessively high temperatures at which some of the reagents tend to decompose or excessively low temperatures at which some of the reagents tend to crystallize or otherwise tend to become inactive. This combinationoccurs very readily and, in general, the components can be mixed at any convenient temperature, preferably within the range of to about C. for a few seconds or for several hours in the presence of a diluent in which both the components are at least partially soluble. Any convenient diluent such as benzene, cyclohexane, toluene, chlorobenzene, methylene chloride, ethylene chloride,

and the like, can be used for this purpose. Halogenated diluents are generally preferred. The mixing of the two catalyst components is carried out in the substantial absence of air or moisture, generally in an inert atmosphere. After the catalytic reaction mixture is formed, it need not be isolated but can be added directly to the olefin reaction zone as a dispersion in its preparation solvent. If desired, the catalyst components can be separately added, in any order, to the reaction zone either in the presence or absence of the feed olefin.

Olefins applicable for use in the process of the invention are nontertiary, nonconjugated olefins including acyclic monoand polyenes having at least three carbon atoms per molecule including cycloalkyl, cycloalkenyl. and aryl derivatives thereof; cyclic monoand polyenes having at least four carbon atoms per molecule including alkyl and aryl derivatives thereof; mixtures of the above olefins; and mixtures of ethylene and the above olefins. Many useful reactions are accomplished with such acyclic olefins having three to 30 carbon atoms per molecule and with such cyclic olefins having four to 30 carbon atoms per molecule. Nontertiary olefins are those olefins wherein each carbon atom, which is attached to other carbon atoms by means of a double bond, is also attached to at least one hydrogen atom.

Some specific examples of acyclic olefins suitable for reactions of this invention include propylene, l-butene,

2-butene, l-pentene, 2-pentene, l-hexene, l,4-hexadiene, 2-heptene, l-octene, 2,5-octadiene, 2-nonene; l-dodecene, Z-tetradecene, l-hexadecene, l -phenylbutene-2, 4-octene, 3-eicosene, 3-hexene, 1,4-pentadiene, 1,4,7-dodecatriene, 2- methyl-4-octene, 4- vinylcyclohexene, l,7-octadiene, 1,5-eicosadiene, 2- triacontene, 2,6-dodecadien e, 1 ,4,7, l 0, l 3-octadecapentaene, 8-cyclopentyl-4,5-dimethyl-1-dece'ne, 6,6-dimethyl-l,4-octadiene, 3-heptene, and the like, and mixtures thereof.

- Some specific examples of cyclic olefins suitable for the reactions of this invention are cyclobutene, cyclopentene, cycloheptene, cyclooctene, vS-n-propylcyclooctene cyclodecene, cyclododecene, 3,3,5,5- tetramethylcyclononene, 3,4,5,6,7-pentaethylcyclodecene, 1,5-cyclooctadiene, 1,5 ,9- cyclododecatriene, l ,4,7, l O-cyclododecatetraene, 6- methyl-6-ethylcyclooctadiene-l,4, and the like, and mixtures thereof.

It will be understood by those skilled in the art that not all olefinic materials will be converted by the present invention with equal effectiveness. The reactions described in the present invention are equilibrium-limited reactions and, barring the selective removal of one or more products from the reaction zone, the extent of conversion will depend upon the thermodynamics of the specific system observed. Thus, conversion of olefinic materials to give specific products can be thermodynamically favored while the reverse reaction is very slow and ineffective. For example l,7-octatriene is converted to equilibrium-favored products such as cyclohexene and ethylene. The reverse reaction of ethylene and cyclohexene, correspondingly, goes very poorly. Other well known factors, such as steric hindrance in bulky molecules, significantly and sometimes drastically affect the rates of reaction of some olefins such that extremely long reaction times are required.

The reaction of symmetrical monoolefins with themselves, to give difierent olefin products, will sometimes proceed very slowly, requiring some double bond migration to take place before the reaction will proceed at a significant rate. For the same reason, the conversion of a mixture of ethylene and a l-olefin, for example, can be more difficult than the conversion of ethylene with an internal olefin, some double bond isomerization also being required in this instance.

It has also been found that branching also retards the olefin reactivity in proportion to its propinquity to the reacting double bond. Analogously, the presence of inert polar substituents on the olefinic compound appears tolerable only if located some distance from the double bond.

Thus, the present invention is directly primarily to the conversion of those olefins or combination of olefins which are capable of undergoing the olefin reaction to a significant degree when contacted with the catalyst of the present invention under reaction conditions suitable for effecting the olefin reaction.

Presently preferred olefinic feed compounds are those contained in the following classes:

1. Acyclic monoolefins, including those with aryl,

cycloalkyl, and cycloalkenyl substituents, having three I to 20 carbon atoms per molecule with no branching closer than about the 3-position to the double bond, no quaternary carbon atoms and no aromatic substitution closer than the 4-position to the double bond, and mixtures of such unsubstituted acyclic monoolefins. Some examples of these are: propylene, pentene-l, pentene- 2, butene-l butene-2, 3-methylbutene-1, hexene-2, octene-4, nonene-2, 4-methylpentene-l, decene-3, 8- ethyldecene-2, dodecene-4, vinylcyclohexane, 4-vinylcyclohexene, eicosenel and the like.

2. A mixture of ethylene and one or more acyclic unsubstituted internal monoolefins of l Some examples of such mixtures are: ethylene and butene-2, ethylene and penteneQ, ethylene and hexane-3, ethylene and heptene-3, ethylene and 4-methylpentene-2, ethylene and octene-4, ethylene and dodecene-4, and the like.

3. Acyclic, non-conjugated polyenes having from five to about 20 carbon atoms per molecule, containing from two to about four double bonds per molecule and having no'double bond with branching nearer than the 3-position to that double bond, and having at least one double bond with no quaternary carbon atoms and no aromatic substitution nearer than the 4-position to that double bond, or mixtures of such polyenes. Some examples are: 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, 2,6-decadiene, l,5,9-'dodecatrien'e, 4-methylheptadiene-l,6, l,7-octadiene, l,6-octadiene, and the like.

4. A mixture of ethylene and one or more acyclic polyenes of (3) which contain at least one internal double bond. Some examples are: ethylene and 1,6-octadiene, ethylene and 1,5-decadiene, and the like.

5 Cyclopentene.

6. Monocyclic and bicyclic monoolefins having seven to 12 ring carbon atoms, including those substituted with up to three alkyl groups having up to about five carbon atoms, with no branching closer than the 3-position and with no quaternary carbon atoms closer than the 4-position to that double-bond, and mixtures of such olefins including mixtures with cyclopentene. Some examples are: cycloheptene, cyclooctene,

4-methylcyclooctene, 3-methyl-5-ethylcyclodecene, cyclononene, cyclododecene, norbornene, and the like.

7. A mixture of one or more of the monocyclic olefins of (6) with either ethylene or with one or more unsubstituted acyclic monoolefins of l Some examples of these are: ethylene and cycloheptene, ethylene and cyclooctene, propylene and cyclodecene, pentene- 2 and cyclooctene, ethylene and cyclododecene, and the like.

8. Monocyclic and bicyclic non-conjugated polyenes having from five to about 12 ring carbon atoms, including those substituted with up to three alkyl groups having up to about five carbon atoms each, having at least one double bond with no branching closer than the 3- position and with no quaternary carbon atoms closer than the 4-position to that double bond, and mixtures thereof. Some examples of these are: 1,5-cyclooctadiene, 1,5 ,9-cyclododecatriene, 1 ,4-cycloheptadiene, norbornadiene, and the like.

9. A mixture of one or more monocyclic polyenes of (8) with one or more acyclic l-olefins having from two to about 10 carbon atoms, having no branching nearer than the 3-position and no quaternary carbon atoms nearer than the 4-position to the double bond. Some examples of these are: l,5-cyclooctadiene and ethylene, 1,5,9-cyclododecatriene and ethylene, 1,5,9- cyclododecatriene and pentene-l and the like.

10. Polar group-substituted olefinic compounds of classes (1) through (9) containing from about five to about 20 carbon atoms per molecule in which the polar group, such as a halogen atom, is sufficiently removed from the active double bond (generally no nearer to the double bond than the 5-position) so as not to interfere with the reaction, and mixtures with unsubstituted members of class (l). Some examples are: 5- chloropentene-l, a mixture of pentene-2 and 5- chloropentenel and the like.

According to the process of the invention, the olefins or mixture of olefins to be converted is contacted with the catalyst system at any convenient temperature, avoiding excessively high temperatures at which some of the reagents tend to decompose, or excessively low temperatures at which some of the reagents tend to crystallize or otherwise tend to become inactive. The process will often be carried out at a temperature preferably within the range of from about 30 to about 150 C., more preferably from to about 75 C., at any convenient pressure which is sufiicient to maintain a liquid phase. The conversion can be carried out in the presence of any diluent such as that used for the catalyst preparation, if desired. Diluents are not essential but are generally preferred and such diluents can include saturated aliphatics and aromatics such as cyclohexane, xylene, isooctane and the like, and halogenated derivatives thereof. .The time of contact will depend upon the desired degree of conversion and the catalysts and olefins utilized, but will, generally, be in the range of from about 0.1 minute to 24 hours, preferably -120 minutes. The proportion of catalyst composition to olefin feed in the reaction zone will generally be in the range of from about 0.001-100 millimoles of the Group VIII metal for each mole of olefin in the reaction zone.

Any conventional contacting technique can be used for the olefin conversion, and batchwise or continuous operation can be utilized. After the reaction period, the products can be separated and/or isolated by conventional means such as by fractionation, crystallization, adsorption, and the like. Unconverted feed material or products not in the desired molecular weight range can be recycled to the conversion zone. If desired, the

catalyst can be destroyed by treatment with a sufficient amount of water or alcohol prior to the separation of the products, to inactivate the catalyst. Otherwise, after separation of the products, the catalyst can be recycled to the reaction zone. Separation of products can be accomplished by distillation, crystallization, evaporation, and the like.

EXAMPLE I Disproportionation of Pentene-l over (Triphenylphosphine) CO)Ru (SnCl )Cl I lMethylaluminum Sesquichloride tenes, andoctenes with a conversion of about 6 per cent.

EXAMPLE II Disproportionation of Pentene-l Over N O-Treated RuCl lMethylaluminum Sesquichloride A 0.4 g quantity of ruthenium trichloride hydrate (38.4 percent Ru) was treated with cc ethanol and the resulting dark brown solution was filtered, and the filtrate was stirred in an atmosphere of nitric oxide at 20 psig for 4 hours at C. The solution became light red in color. The solution was diluted with about 25 cc heptane and the volatiles were slowly removed in vacuo leaving a dark red oil. The oil was treated with about 23 I cc of chlorobenzene which yielded a purple-red solution.

The above solution was decanted into a dry 7-ounce pressure bottle under nitrogen and 5 cc pentene-l was added. The mixture was then cooled in an ice bath and treated with 3 cc of a 0.5 molar methylaluminum Sesquichloride solution in chlorobenzene. The mixture was removed from the ice bath, stirred for 2 hours at room temperature, and hydrolyzed by the addition of water. Analysis of the organic phase of the reaction mixture showed the presence of ethylene, propylene, butenes, isomerized pentenes, hexenes, heptenes, octenes nonenes, and decenes. The conversion of the pentene-l to other olefin products was about 5-6 per cent.

EXAMPLE n1 Disproportionation of Pentene-l Over NOand Sesquichloride In a manner similar to that of Example II, 0.4 g of ruthenium trichloride hydrate and 30 cc ethanol were stirred in an atmosphere of NO, at 20 psig, for 2.5 hours at 75 C. The hot reaction mixture was then filtere'd into a flask containing 0.8 g triphenylphosphine and the resulting mixture was treated at 70 C. for about minutes. The mixture was allowed to stand one day at room temperature during which time a solid precipitated. The solidwas removed by filtration, washed with ethanol and ether, and dried in vacuo, yielding a pale yellow-green compound melting at 2 l 8-224 C.

A 0.2 g quantity of theabove-prepared ruthenium compound was tested for pentene-l disproportionation in a manner essentially identical with that of Example I] in a system which also contained 10 cc chlorobenzene, 3 cc of the methylaluminum sesquichloride solution, and 4 cc of pentene-1. After about 18 hours at room temperature, analysis of the reaction mixture showed the presence of ethylene, propylene, butenes, isomerized pentenes, hexenes, heptenes, and octenes. The conversion of pentene-l was about 10 per cent.

EXAMPLE IV Disproportionation of Pentene-l Over (NO) RhCl/Met hylaluminum Sesquichloride A 0.1, g quantity of (NOhRhCl, 10 cc of chlorobenzene, and 0.2 cc of methylaluminum sesquichloride were mixed at room temperature in a dry 7-ounce pressure vessel under a nitrogen atmosphere. The dark brown rhodium complex dissolved EXAMPLE V Disproportionation'of Pentene-l Over RhCl Treated with NO AND Triphenylphosphine A 0.4 g quantity of RhCl '3H O and 30 cc of ethanol were heated at 75 C. for 2.5 hours under a 20 psig pressure of nitric oxide. The hot reaction mixture was filtered, and the filtrate was treated with 0.8 g of triphenylphosphine for 15 minutes at 70 C. This reaction mixture yielded a reddish-brown precipitate on standing. The precipitate had a melting point of 233-236 C. This material was (triphenylphosphine) Rh(NO)Cl After drying, a 0.2 gram quantity of the above solid was placed in a 7-ounce pressure vessel under a nitrogen atmosphere together with 10 cc chlorobenzene. The mixture was cooled to 0 C. and treated with 1.5 millimoles of methylaluminum sesquichloride, and 4 cc of pentene-1. The reactor was removed from the ice bath and allowed to stand overnight.

The reaction mixture was hydrolyzed and the organic phase was analyzed by gas-liquid chromatography which indicated the presence of ethylene, propylene, butenes, isomerized pentenes, hexenes, heptenes, and

octenes. About 5 per cent of the pentene feed was converted.

Equivalent results were obtained in a similar test in which the catalyst was prepared utilizing the nitric oxide treatment after the triphenylphosphine reagent was present.

EXAMPLE VI Disproportionation of Hexene-l Over [(1r-allyl) RhCl],/ethylaluminum Sesquichloride reaction mixture. The conversion of hexenes was about 40-50 per cent.

EXAMPLE v11 Conversion of Pentene-Z Over [Fe(NO) Cl] lMethylaluminum Sesquichloride A 0.2 g quantity of [Fe(NO) Cl] was charged into a 7-ounce pressure bottle under a nitrogen atmosphere, followed by 10 cc chlorobenzene, 6.0 cc of a 1 molar solution of methylaluminum sesquichloride in chlorobenzene, and 6 'cc pentene-2 at room temperature. After being stirred for about 5% hours at room temperature, the reaction mixture, when analyzed, in-

dicated about a l per cent conversion of pentene-2 to butenes and hexenes.

EXAMPLE Vlll Conversion of Pentene-2 Over NO-treated (Triphenylphosphine) oCl lMethylaluminum Sesquichloride A 0.3 g quantity of (triphenylphosphine) CoCl was charged into a 7-ounce pressure bottle under an inert gas atmosphere followed by 15 cc of chlorobenzene. The bottle was then pressured with nitric oxide at 20 psig for 3,3 hours at room temperature. After venting the bottle and flushing with nitrogen, 6 ccof a 0.5 molar solution of methylaluminum sesquichloride and 5 cc of pentene-2 were then added to the solution which had been cooled to 0 C. The mixture was then stirred for 2 hours at 0 C., followed by hydrolysis by the addition of water. Analysis of the organic phase showed the presence of hexenes, heptenes, octenes, decenes, and unreacted pentene.

EXAMPLE IX Conversion of Pentene-Z Over NO-treated and Triphenylphosphine-treated IrCl /Methylaluminum Sesquichloride A 0.4 g quantity of IrCl hydrate was mixed with 30 cc ethanol and contacted with psig nitric oxide for 4 hours and at 75 C. The mixture was then filtered hot, the filtrate being allowed to contact 0.8 g of triphenylphosphine. This mixture was heated at 70 C. for 15 minutes and then allowed to stand overnight at room temperature. The mixture, containing a dark brown solid, was filtered, washed with ethanol and ether, and g EXAMPLE X material was (triphenylphosphinehl Preparation of (Triphenylphosphine Rh(NO) (NO )Cl A 0.5 g quantity of (triphenlyphosphine RhCl was dissolved in 15 ml benzene in a dry 7 oz. reaction flask which had been flushed with nitrogen. The flask was then flushed with NO and then subjected to 20 psig NO pressure with stirring for 0.5 hr. at room temperature during which time the solution turned a dark green. The solution was then chilled and diluted with 10 ml npentane resulting in the precipitation of green crystals. Isolation by filtration, washing, and drying yielded 0.2 g ofa material which had a melting point of l54l 56 C (with decomposition).

Elemental analysis showed the following in weight percent.

I Found .9 Calculated .8

An infrared spectrum of the material (in KBr disc) EXAMPLE XI Preparation of (Triphenylarsine Rh(NO) (NO )CI In a manner essentially identical to that of the previous example 0.3 g of (triphenylarsine) RhCl was treated with NO in benzene solution for 35 minutes. A 0.20 g quantity of olive colored (triphenylarsine),Rh (NO) (NO )Cl was isolated. The re-crystallized material melted at 205208 C.

EXAMPLE XII Preparation of (Triphenylphosphine) Rh(NO) (NO- )Cl A 0.32 g quantity of (triphenylphosphine) Rh(CO) (N0 was dissolved in 10 ml chloroform under a nitrogen atmosphere. A 5.0 ml quantity of a 0.1 M solution of nitrosyl chloride in benzene was added resulting in a rapid change of color from the clear yellow to a dark green. The mixture was stirred for an hour at room temperature and filtered. To the filtrate was added 20 ml n-pentane and the mixture was cooled, resulting in the formation of green crystals of (triphenylphosphine Rh(NO) (NO )Cl which were isolated by filtration yielding a total of 0.22 g of this complex[ EXAMPLE XIII Preparation of (Triphenylarsine) Rh(NO) (NO )Cl In a manner similar to that of the preceding example, 0.5 g of (triphenlarsine) Rh(CO)Cl was treated with N0 gas in 20 ml benzene for 25 min. at room temperature. To this solution was then added 20 cc n-pentane resulting in the formation of a precipitate. A 0.4 g quantity of (triphenylarsine Rh(NO) (NO )Cl was isolated, melting at 208-2l0 C (dec.). The elemental analysis and infrared spectrum were consistent with the indicated identity of the compound.

EXAMPLE XIV Preparation of (Triphenylphosphine) Rh(NO) (NO )Cl In a manner similar to that of the preceding example 0.5 g (triphenlphosphine) Rh(CO)Cl in 20 ml benzene were treated with 20 psig NO for 20 min. at room temperature. The addition of 20 ml n-pentane resulted in precipitation of a greed solid, which, after isolation by filtration, washing, and drying, weighed 0.50 g. The elemental analysis and infrared spectrum of this solid was consistent with the formula -(triphenylphosphine) Rh(NO) (NO- )Cl and a mixed melting point of this solid and .a previously identified sample showed no depression.

EXAMPLE Xv Preparation of (Triephenylphosphine Ir(NO)Cl A 0.4 g quantity of IrCl -hydrate (53.02 percent Ir) was dissolved in 30 ml ethanol and placed under 20 psig NO pressure for 2.5 hr at C. The reaction mixture was then filtered hot onto 1.5 g triphenylphosphine. The complex (triphenlphosphine) Ir(NO)Cl was precipitated from this hot mixture and was isolated by filtration, washing, and drying. A second crop of crystals of this material was obtained by cooling the filtrate.

EXAMPLE XVI Preparation of (Triphenylphosphine) Rh(NO)Cl A 0.2 g quantity of (triphenylphosphine);,RhCl was mixed with 10 ml methylene chloride and 0.15 ml of a IM solution of NOCl in chlorobenzene in a nitrogenpurged 7 oz reaction flask. The mixture was stirred for about 30 minutes at room temperature, then diluted with methanol resulting in the precipitation of a rustbrown solid. The material was isolated by filtration, washing, and drying, yielding 0.1 g of (triphenylphosphine Rh(NO)Cl which, after recrystallization, had a melting point of 232-234 C. The elemental analysis and infrared spectrum of this material were consistent with the above formula.

In the practice of the process of the invention, the feed olefins, catalyst and operating conditions disclosed include combinations wherein solid, rubbery materials are produced; for example, if a propylene feed and a suitable aluminum-containing adjuvant such as an organoaluminum dihalide or an organoaluminum sesquihalide are used, a solid, rubbery material is produced having characteristics of ethylene-propylene rubber. This rubbery material is useful in the manufacture of tires, wire coating, footwear and other industrial products. 1

The homogeneous catalysts of this invention can be deposited upon a suitable support or carrier and used in the olefin reaction, preferably where the olefin feed is in the vapor'phase. Catalyst supports include solid, inorganic or organic materials conventionally used as catalyst supports or carriers such as silica, alumina, silica-alumina, titania, boria, zeolites, ion exchange resins,- solid polymers containing functional groups such asthose prepared by the polymerization of 4- vinylpyridine, vinyldimethylphosphine, and the like.

The support can be impregnated with the homogeneous catalyst by wetting the support with a solution of the catalyst in a solvent which is then evaporated. Among solvents suitable are relatively low-boiling organic solvents such as pentane, methylene chloride, cyclohexane, and the like. The amount of homogeneous catalyst added to the support will be from 0.1 to about 30 weight per cent of the total of the catalyst and support. If the support is to be activated by calcination, it is usually activated prior to the impregnation step.

impregnation and evaporation conditions in preparing the catalyst are conventional, being carried out at temperatures up to about 150 C. Operating conditions in carrying out the olefin reaction are the same for the supported and the non-supported homogeneous catalyst systems We claim: 1. A process for the conversion of at least one nonconjugated feed olefin having at least three carbon atoms according to the olefin reaction under conditions suitable for said olefin reaction, wherein the conversion according to the olefin reaction can be visualized as comprising the reaction between two first pairs of carbon atoms, the two carbon atoms of each first pair being connected by an olefinic double bond, to form two new pairs from the carbon atoms of said first pairs, the two carbon atoms of each said new pairs being connected by olefinic double bond,

which process comprises contacting said n'onconjugated feed olefin with a catalyst which forms on admixture of i a. a complex which forms, under complex forming conditions, of a compound of metal which is iron, ruthenium, osmium, rhodium or iridium with at least one ligand-forming material; and

b. an aluminum-containing catalytic adjuvant selected from the group consisting of l. R AlX,, 2. a mixture ofcompounds of l 3. a mixture of one or more R AlX, or AlX; compounds with one or more compounds having the formula R M X and 4. an AlX compound wherein each R is an aromatic or saturated aliphatic hydrocarbon radical having up to 20 carbon atoms including alkoxy and halo derivatives thereof, preferably an alkyl radical having up to 10 carbon atoms; each R is hydrogen or R; each X is a halogen; each M is a metal of Group IA, HA, IIB, or HIA; e is l, 2 or 3,fis O, 1 or 2, the sum ofe andfbeing 3;g is 1, 2 or 3, h is 0, l or 2, the sum ofg and It being equal to the valence of M wherein said ligand-forming material comprises NO; NOX; R Q; R QQR R NR --NR C0; unsubstituted or R -substituted pyridines; unsubstituted or R -substituted 2,2'-bipyridines; unsubstituted or R-substituted cyclopentadienyl radical-containing com-- pounds;

RSR, R (CN), ,I R (COO+ radical-containing compound; 1,5-cyclooctadiene; dicyclopentadiene; or norbornadiene, wherein x is halogen, R is an aromatic or saturated aliphatic hydrocarbon radical, including alkoxy and halo-substituted radicals, having up to 20 carbon atoms, R is hydrogen or R, R is a divalent R radical, R is a divalent saturated or ethylenically unsaturated aliphatic hydrocarbon radical having four to 10 carbon atoms, R is hydrogen or a methyl radical; R is an aromatic, saturated or ethylenically unsaturated aliphatic radical having up to 30 carbon atoms, Qis phosphorus, arsenic or antimony, and y is an integer from 1 to 2.

2. The process according to claim 1. wherein the compound of the metal is an iron, ruthenium osmium, cobalt, rhodium, or iridium halide, cyanide, thiocyanate, cyanate, thriclorostannate, or organic carboxylate wherein the organic carboxylate has up to about 30 carbon atoms; the number of ligand-forming materials and the number of halide, cyanide, thiocyanate, cyanate, thrichlorostannate, or organic carboxylate groups present in the complex is not greater than the number required for the metal to achieve the closed shell electronic configuration of the next higher atomic number inert gas; when the metal is ruthenium or'osmiurn, the number of NO groups is O-2; and when the metal is iron, two NO groups are present.

3. A process according to claim 1 wherein the catalyst forms on admixture of a. a metal complex according to the formula (R Q M (NO) (NOQX wherein M is rhodium or iridium, Q is phosphorus or arsenic, X is a halogen, and R is an aromatic or saturated aliphatic hydrocarbon radical having 20 carbon atoms including alkoxy and halo derivatives thereof; with b. an aluminum-containing adjuvant selected from the group consisting of l. R AlX,, and 2. a mixture of compounds of l wherein R and X are as defined above, and e is 1, 2 or 3,fis 0, l or 2, the sum ofeandfbeing 3.

cyclic mono-and polyenes having at least quaternary carbon atoms per molecule including alkyl and aryl derivatives thereof, mixtures of the above olefins or mixtures of ethylene and the above olefms.

5. The process of claim 3 wherein the catalyst consists essentially of (triphenylphosphine Rh(NO) (NO )Cl and ethylaluminum dichloride.

6. A process according to claim 1 wherein said nonconjugated feed olefin hydrocarbon is selected from the group consisting of 1. acyclic monoolefins, including those with aryl,

cycloalkyl, and cycloalkenyl substituents, having three to ab'out20 carbon atoms per molecule, with no branching closer to the double bond than the 3- position and no quanternary carbon atom or aromatic substitution closer to the double bond than the 4-position, and mixtures of such unsubstituted acyclic monoolefins;

. a mixture of ethylene and one or more acyclic, un-

substituted, internal monoolefins of 1 3. acyclic, nonconjugated polyenes having five to about 20 carbon atoms per molecule, containing two to about four double bonds per molecule and having at least one double bond with no branching nearer to it than the 3-position and no quaternary carbon atom nearer to it than the 4-position, and mixtures of such polyenes;

4. a mixture of ethylene and one or more acyclic polyenes of (3) which contains at least one internal double bond;

. cyclopentene;

. cyclic and bicyclic monoolefins having seven to about 12 ring carbon atoms; including those substituted with up to three alkyl groups having up to about five carbon atoms each with no branching closer to the double bond than the 3-position and with no quaternary carbon atoms closer to th double bond than the 4-position;

with ethylene or with one or more unsubstituted, acyclic monoolefins of l cyclic and bicyclic nonconjugated polyenes having five to about 12 ring carbon atoms including-those substituted with up to 3 alkyl groups having up to five carbon atoms each, with at least one of the double bonds having no branching closer than the 3-position and no quaternary carbon atom closer than the 4position;

. a mixture of one or more monocyclic polyenes of (8) with one or more acyclic l-olefins having from two to about 10 carbon atoms with no branching closer to the double bond than the 3-position and no quaternary carbon atom closer to the double bond than the 4-position;

l0. polar group-substituted olefinic compounds of classes (1) through (4) and (6) through (9) containing about five to carbon atoms per molecule in which the polar group is no closer to the double bond than the 5-position, and mixtures with unsubstituted member of(l 7. The process of claim 1 wherein the molar ratio of the (b) component of the catalyst to the (a) component of the catalyst is in the range of from about 0.1:] to about 20:1.

8. The process of claim 1 wherein said conditions for said olefin disproportionation reaction include a tema mixture of one or more monocyclic olefins of (6).

perature in the range of about -30 to about C, a pressure sufi'icient to maintain the liquid phase, a time of contact in the range of about 0.1 to about hours, and a ratio of catalyst composition to olefin feed of about 0.001 to about 100 millimoles of Group VIII metal for each mole of olefin feed.

9. The process of claim 1 wherein the conversion is accomplished in the presence of an inert diluent in which both of the (a) and (b) components of the catalyst are at least partially soluble.

10. The process of claim 1 wherein the catalyst further includes a solid inorganic or organic support or carrier selected from the group consisting of silica, alumina, silica-alumina, titania, boria, zeolites, ion exchange resins, a solid polymer of 4-vinylpyridine and a solid polymer of vinyl dimethylphosphine.

11. A process for the conversion of at least one nonconjugated feed olefin having at least three carbon atoms according to the olefin reaction under conditions suitable for said olefin reaction, wherein the conversion according to the olefin reaction can be visualized as comprising the reaction between two first pairs of carbon atoms, the two carbon atoms of each first pair being connected by an olefinic double bond,- to form two new pairs from the carbon atoms of said first pairs, the two carbon atoms of each said new pairs being con-. nected by an olefinic double bond,

which process comprising contacting said nonconjugated feed olefin with a catalyst which forms on admixture of a complex which forms, under complex forming conditions, a compound of the metal iron or cobalt subgroups of Group VIII with at least one ligandforming material wherein said complex can be represented by the formula [(L) (Y) M Z wherein M is a metal of the iron or cobalt sub-' groups of Group VIII, namely, iron, ruthenium, osmium, cobalt, rhodium, and iridium; each Z is halogen or CN, SCN, OCN, SnCl or an organic acid radical having up to about 30 carbon atoms; each (Y) is NO; each (L) is a ligand represented by R 0, R2QQR R NR CO, R NR NR unsubstituted or R -substituted pyridines, unsubstituted or R -substituted 2,2'-bipyridines, unsubstituted or R-substituted rr-cyclopentadienyl radicals,

R s ll R (CN R (CO O '1,s-y1b01adiai dicyclopentadiene, or norbornadiene; a is 0-6, I; is 1-2, y is l-2, c is l-3, d is 0-6, x is a number which is indicative of the polymeric state of the complex, and wherein the number of (L), (Y) and Z groups present in the complex is not greater than the number required for the metal to achieve the closed shell electronic configuration of the next higher atomic number inert gas; when M is Ru or Os, 1; is 0-2; when M is Fe, b is 2; R is an aromatic or saturated aliphatic hydrocarbon radical, including alkoxy and halo-substituted radicals, having up to 20 carbon atoms; R is hydrogen or R; R is a divalent R radical; R is a divalent saturated or ethylenically unsaturated aliphatic hydrocarbon radical having from four to 10 carbon atoms; R is hydrogen or i a methyl radical; R is anaromatic, saturated aliphatic,

or ethylenically unsaturated aliphatic radical having up to 30 carbon atoms; and Q is phosphorus arsenic, or antimony;

said aluminum-containing catalytic adjuvant is selected from the group consisting of 1. R A1X,,

2. a mixture of compounds of 1 3. a mixture of one or more R AiX, or AlX compounds with one or more compounds having the formula R,,M,,X or an AlX compound wherein each R is an aromatic or saturated aliphatic hydrocarbon radical having up to carbon atoms including alkoxy and halo derivatives thereof, preferably an alkyl radical having up to 10 carbon atoms; each R is hydrogen or R; each X is a halogen; each M is a metal of Group IA, IlA, llB, or lllA; e is 1, 2 or 3,fis 0, 1 or 2, the sum ofe andfbeing 3; g is-l, 2 or 3, h is 0,1 or 2, the sum of g and h being equal to the valence of M. v

12. The process of claim 10 wherein the olefin hydrocarbon is pentene-l hexene-l or pentene-2.

13. The process of claim 12 wherein the (a) component is (triphenylphosphine).,(CO) Ru (SnCl )Cl and the (b) component sesquichloride.

is methylaluminum RhCl and the '(b) component is methylaluminum sesquichloride.

18. The process of claim 12 wherein the (a) component is [Fe(NO) Cl] and the (b) component is V methylaluminum sesquichloride.

19. The process of claim 12 wherein the (a) component is NO and triphenylphosphine complexed with lrCl and the (b) component is methylaluminum sesquichloride.

v 20. The process of claim 12 wherein the (a) component uses NO and triphenylphosphine complexed with CoCl and the (b) component is methylaluminum sesquichloride. v

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. I 3,721,718

DATED March 20, 1973 lN\/ ENTOR(S) I William B. Hughes, Ernest A. Zuech It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 18, claim 1, line 21, delete "R (CO0)-" and ub ti therefore R (CO0)-y Column 18, claim 4, line 67, delete "quaternary" and substitute therefore 4 Column 20, claim 11, line 53, delete "R '(COO)-" and sub tit therefore R (C()())-y Column 21, claim 12, line 22, delete "l0" and substitute therefore l1 Column 22, claims l4, l5, l6, l7,' l8, l9, and 20, line 1 in a h occurrence, delete "l2" and substitute therefore ll Signed and Scaled this nineteenth Day of July 1977 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Al l g oflicer Commissioner of Patents and Trademarks UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,721,718 Dated March 20, 1973 Inventor(s) Wllllam Hughes et 81.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Cover page 1, line 4,- in the title, after "Rh" and before "OR" insert Co Signed and Scaled this Eighteenth Day Of October 1977 [SEAL] Attest:

RUTH c. MASON LUTRELLE F. PARKER Attesting Ojficer Acting Commissioner of Patents and Trademarks 

2. a mixture of compounds of (1),
 2. The process according to claim 1 wherein the compound of the metal is an iron, ruthenium osmium, cobalt, rhodium, or iridium halide, cyanide, thiocyanate, cyanate, thriclorostannate, or organic carboxylate wherein the organic carboxylate has up to about 30 carbon atoms; the number of ligand-forming materials and the number of halide, cyanide, thiocyanate, cyanate, thrichlorostannate, or organic carboxylate groups present in the complex is not greater than the number required for the metal to achieve the closed shell electronic configuration of the next higher atomic number inert gas; when the metal is ruthenium or osmium, the number of NO groups is 0-2; and when the metal is iron, two NO groups are present.
 2. a mixture of compounds of (1), wherein R and X are as defined above, and e is 1, 2 or 3, f is 0, 1 or 2, the sum of e and f being
 3. 2. a mixture of ethylene and one or more acyclic, unsubstituted, internal monoolefins of (1);
 2. a mixture of compounds of (1),
 3. a mixture of one or more ReAiXf or AlX3 compounds with one or more compounds having the formula R1gM1hX , or
 3. acyclic, nonconjugated polyenes having five to about 20 carbon atoms per molecule, containing two to about four double bonds per molecule and having at least one double bond with no branching nearer to it than the 3-position and no quaternary carbon atom nearer to it than the 4-position, and mixtures of such polyenes;
 3. A process according to claim 1 wherein the catalyst forms on admixture of a. a metal complex according to the formula (R3Q1)2M2(NO) (NO2)X wherein M2 is rhodium or iridium, Q1 is phosphorus or arsenic, X is a halogen, and R is an aromatic or saturated aliphatic hydrocarbon radical having 20 carbon atoms including alkoxy and halo derivatives thereof; with b. an aluminum-containing adjuvant selected from the group consisting of
 3. a mixture of one or more ReAlXf or AlX3 compounds with one or more compounds having the formula R1gM1Xh, and
 4. an AlX3 compound wherein each R is an aromatic or saturated aliphatic hydrocarbon radical having up to 20 carbon atoms including alkoxy and halo derivatives thereof, preferably an alkyl radical having up to 10 carbon atoms; each R1 is hydrogen or R; each X is a halogen; each M1 is a metal of Group IA, IIA, IIB, or IIIA; e is 1, 2 or 3, f is 0, 1 or 2, the sum of e and f being 3; g is 1, 2 or 3, h is 0, 1 or 2, the sum of g and h being equal to the valence of M1; wherein said ligand-forming material comprises NO; NOX; R3Q; R2Q-QR2; R2N-R2-NR2; CO; unsubstituted or R5-substituted pyridines; unsubstituted or R5-substituted 2,2''-bipyridines; unsubstituted or R-substituted cyclopentadienyl radical-containing compounds; R-S-R, R5(CN)y, R5(COO radical-containing compound; 1,5-cyclooctadiene; dicyclopentadiene; or norbornadiene, wherein x is halogen, R is an aromatic or saturated aliphatic hydrocarbon radical, including alkoxy and halo-substituted radicals, having up to 20 carbon atoms, R1 is hydrogen or R, R2 is a divalent R radical, R is a divalent saturated or ethylenically unsaturated aliphatic hydrocarbon radical having four to 10 carbon atoms, R4 is hydrogen or a methyl radical; R5 is an aromatic, saturated or ethylenically unsaturated aliphatic radical having up to 30 carbon atoms, Q is phosphorus, arsenic or antimony, and y is an integer from 1 to
 2. 4. The process of claim 1 wherein said nonconjugated feed olefin is an acyclic mono- and polyenes having at least three carbon atoms per molecule including cycloalkyl, cycloalkenyl, and aryl derivatives thereof, cyclic mono- and polyenes having at least quaternary carbon atoms per molecule including alkyl and aryl derivatives thereof, mixtures of the above olefins or mixtures of ethylene and the above olefins.
 4. a mixture of ethylene and one or more acyclic polyenes of (3) which contains at least one internal double bond;
 4. an AlX3 compound wherein each R is an aromatic or saturated aliphatic hydrocarbon radical having up to 20 carbon atoms including alkoxy and halo derivatives thereof, preferably an alkyl radical having up to 10 carbon atoms; each R1 is hydrogen or R; each X is a halogen; each M1 is a metal of Group IA, IIA, IIB, or IIIA; e is 1, 2 or 3, f is 0, 1 or 2, the sum of e and f being 3; g is 1, 2 or 3, h is 0, 1 or 2, the sum of g and h being equal to the valence of M1.
 5. cyclopentene;
 5. The process of claim 3 wherein the catalyst consists essentially of (triphenylphosphine)2Rh(NO) (NO2)Cl and ethylaluminum dichloride.
 6. A process according to claim 1 wherein said nonconjugated feed olefin hydrocarbon is selected from the group consisting of
 6. cyclic and bicyclic monoolefins having seven to about 12 ring carbon atoms; including those substituted with up to three alkyl groups having up to about five carbon atoms each with no branching closer to the double bond than the 3-position and with no quaternary carbon atoms closer to the double bond than the 4-position;
 7. a mixture of one or more monocyclic olefins of (6) with ethylene or with one or more unsubstituted, acyclic monoolefins of (1);
 7. The process of claim 1 wherein the molar ratio of the (b) component of the catalyst to the (a) component of the catalyst is in the range of from about 0.1:1 to about 20:1.
 8. cyclic and bicyclic nonconjugated polyenes having five to about 12 ring carbon atoms including those substituted with up to 3 alkyl groups having up to five carbon atoms each, with at least one of the double bonds having no branching closer than the 3-position and no quaternary carbon atom closer than the 4position;
 8. The process of claim 1 wherein said conditions for said olefin disproportionation reaction include a temperature in the range of about -30* to about 75* C, a pressure sufficient to maintain the liquid phase, a time of contact in the range of about 0.1 to about 100 hours, and a ratio of catalyst composition to olefin feed of about 0.001 to about 100 millimoles of Group VIII metal for each mole of olefin feed.
 9. The process of claim 1 wherein the conversion is accomplished in the presence of an inert diluent in which both of the (a) and (b) components of the catalyst are at least partially soluble.
 9. a mixture of one or more monocyclic polyenes of (8) with one or more acyclic 1-olefins having from two to about 10 carbon atoms with no branching closer to the double bond than the 3-position and no quaternary carbon atom closer to the double bond than the 4-position;
 10. polar group-substituted olefinic compounds of classes (1) through (4) and (6) through (9) containing about five to 20 carbon atoms per molecule in which the polar group is no closer to the double bond than the 5-position, and mixtures with unsubstituted member of (1).
 10. The process of claim 1 wherein the catalyst further includes a solid inorganic or organic support or carrier selected from the group consisting of silica, alumina, silica-alumina, titania, boria, zeolites, ion exchange resins, a solid polymer of 4-vinylpyridine and a solid polymer of vinyl dimethylphosphine.
 11. A process for the conversion of at least one nonconjuGated feed olefin having at least three carbon atoms according to the olefin reaction under conditions suitable for said olefin reaction, wherein the conversion according to the olefin reaction can be visualized as comprising the reaction between two first pairs of carbon atoms, the two carbon atoms of each first pair being connected by an olefinic double bond, to form two new pairs from the carbon atoms of said first pairs, the two carbon atoms of each said new pairs being connected by an olefinic double bond, which process comprising contacting said nonconjugated feed olefin with a catalyst which forms on admixture of a. a complex which forms, under complex forming conditions, a compound of the metal iron or cobalt subgroups of Group VIII with at least one ligand-forming material wherein said complex can be represented by the formula ((L)a(Y)bMcZd)x wherein M is a metal of the iron or cobalt subgroups of Group VIII, namely, iron, ruthenium, osmium, cobalt, rhodium, and iridium; each Z is halogen or CN, SCN, OCN, SnCl3, or an organic acid radical having up to about 30 carbon atoms; each (Y) is NO; each (L) is a ligand represented by R3Q, R2Q-QR2, R2NR1, CO, R2N-R2-NR2, unsubstituted or R5-substituted pyridines, unsubstituted or R -substituted 2,2''-bipyridines, unsubstituted or R-substituted pi -cyclopentadienyl radicals, R-S-R, R5(CN)y, R5(COO, 1,5-cyclooctadiene, dicyclopentadiene, or norbornadiene; a is 0-6, b is 1-2, y is 1-2, c is 1-3, d is 0-6, x is a number which is indicative of the polymeric state of the complex, and wherein the number of (L), (Y) and Z groups present in the complex is not greater than the number required for the metal to achieve the closed shell electronic configuration of the next higher atomic number inert gas; when M is Ru or Os, b is 0-2; when M is Fe, b is 2; R is an aromatic or saturated aliphatic hydrocarbon radical, including alkoxy and halo-substituted radicals, having up to 20 carbon atoms; R1 is hydrogen or R; R2 is a divalent R radical; R3 is a divalent saturated or ethylenically unsaturated aliphatic hydrocarbon radical having from four to 10 carbon atoms; R4 is hydrogen or a methyl radical; R5 is an aromatic, saturated aliphatic, or ethylenically unsaturated aliphatic radical having up to 30 carbon atoms; and Q is phosphorus arsenic, or antimony; said aluminum-containing catalytic adjuvant is selected from the group consisting of
 12. The process of claim 10 wherein the olefin hydrocarbon is pentene-1, hexene-1, or pentene-2.
 13. The process of claim 12 wherein the (a) component is (triphenylphosphine)4(CO)2Ru2(SnCl3)Cl3 and the (b) component is methylaluminum sesquichloride.
 14. ThE process of claim 12 wherein the (a) component is NO complexed with RuCl3, and the (b) component is methylaluminum sesquichloride.
 15. The process of claim 12 wherein the (a) component is NO and triphenylphosphine complexed with RuCl3 and the (b) component is methylaluminum sesquichloride.
 16. The process of claim 12 wherein the (a) component is (NO)2RhCl and the (b) component is methylaluminum sesquichloride.
 17. The process of claim 12 wherein the (a) component is NO and triphenylphosphine complexed with RhCl3 and the (b) component is methylaluminum sesquichloride.
 18. The process of claim 12 wherein the (a) component is (Fe(NO)2Cl)2 and the (b) component is methylaluminum sesquichloride.
 19. The process of claim 12 wherein the (a) component is NO and triphenylphosphine complexed with IrCl3 and the (b) component is methylaluminum sesquichloride.
 20. The process of claim 12 wherein the (a) component uses NO and triphenylphosphine complexed with CoCl2 and the (b) component is methylaluminum sesquichloride. 